CN102470342A - Oil absorbent and oil absorbent manufacturing method - Google Patents

Oil absorbent and oil absorbent manufacturing method Download PDF

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Publication number
CN102470342A
CN102470342A CN2009801603624A CN200980160362A CN102470342A CN 102470342 A CN102470342 A CN 102470342A CN 2009801603624 A CN2009801603624 A CN 2009801603624A CN 200980160362 A CN200980160362 A CN 200980160362A CN 102470342 A CN102470342 A CN 102470342A
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China
Prior art keywords
oil content
inorganic particulate
polymer
sorbing material
water
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CN2009801603624A
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CN102470342B (en
Inventor
深谷太郎
藤枝新悦
村井伸次
铃木昭子
辻秀之
河野龙兴
山田有纱
足利伸行
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Toshiba Corp
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Toshiba Corp
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Compounds Of Iron (AREA)
  • Glanulating (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Disclosed are an oil absorbent and an oil absorbent manufacturing method for the purpose of recovering oil from water. The oil absorbent is characterized in comprising inorganic particles and a polymer formed on the surface of or between these inorganic particles; the content rate of inorganic particles is no less than 50 vol% and no more than 97 vol% with respect to the inorganic particles and the polymer; and the surface area of the inorganic particles is no less than 30% and no more than 60% with respect to the cross section of the inorganic particles and the polymer. Furthermore, the manufacturing method for oil absorbent particles has a step wherein inorganic particles, a polymer, and a solvent are mixed and a slurry solution is prepared, and a step wherein the slurry solution is sprayed in an environment wherein the temperature is at least 30 DEG C higher than the boiling point of the solvent.

Description

The manufacturing approach of oil content sorbing material and oil content sorbing material
Technical field
The present invention relates to be used for reclaiming the oil content sorbing material of oil content and the manufacturing approach of oil content sorbing material from water.
Background technology
In recent years, along with the increase of the prosperity of industry and population and require effectively to utilize water resource.Therefore, useless water reuse such as industrial water drainage is extremely important.In order to realize above purpose, need purify water, promptly from water, separate other material.
As from liquid with the method for other separating substances, known have a whole bag of tricks, for example can enumerate film separation, centrifugation, charcoal absorption, ozone treatment, flocculation and utilize the regulation sorbing material to remove suspended solid etc.Through such method, can the chemical substance that phosphorus contained in the water or nitrogen etc. have greater environmental impacts be removed, can remove being scattered in oils in the water, clay etc.
Wherein, film the most often is separated into one of method of using, but exists in the problem that life-span of pore, the film of oil easy blocking film when removing the oils that is dispersed in the water shortens easily.Therefore, film separates the oils that is not suitable for except that in anhydrating under a lot of situation.Therefore,, for example can enumerate following method: utilize the last buoyancy of heavy oil, collect the heavy oil that floats over water surface through the oil fence of setting waterborne, from the method for attracted by surfaces and recovery as the method for from the water that comprises oils such as heavy oil, removing these oils; Or lay the hydrophobic material that heavy oil is had adsorptivity on the water, absorption is also reclaimed the method etc. of heavy oil.
From this viewpoint, in recent years, carried out following trial: in using the oil content sorbing material and being immersed in the water that is dispersed with oils, above-mentioned oils is adsorbed on the oil content sorbing material, it is removed from water.For example, in patent documentation 1, disclose the oil content sorbing material that organic matter such as using on the surface of magnetic particle polymeric adsorbent forms, from water, adsorbed the technology of removing oil content.But, in the method, has dispersed low, above-mentioned functions property particle Shen in water and fall or swim, thereby the absorption that can not carry out oil content is effectively removed in the tendency on surface.
In addition, in patent documentation 2, disclose the adsorpting polymerization thing that uses as the oil content sorbing material of possess hydrophilic property block and lipophile block and made oil adsorb the method for then this adsorpting polymerization thing being removed from water.But, in such method, there is the labor intensive of separating of not only adsorpting polymerization thing and water, and adsorbed the oil bodying thing and the softening intensity of oily sorbing material that causes takes place reduce, thus the problem of operation property variation.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication sho 60-97087 number
Patent documentation 2: japanese kokai publication hei 07-102238 number
Summary of the invention
Invent problem to be solved
The present invention in view of the above problems, its purpose is, a kind of oil content adsorbance height and high oil content sorbing material of intensity in water is provided.
The means that are used to deal with problems
The oil content sorbing material of a form of the present invention is characterised in that; It has inorganic particulate and is formed at the polymer between this inorganic particulate surface or this inorganic particulate; The containing ratio of said inorganic particulate is 50 volume %～97 volume % with respect to said inorganic particulate and said polymer, and the area of said inorganic particulate is 30%～60% with respect to the cross section of said inorganic particulate and said polymer.
The effect of invention
According to the present invention, a kind of oil content adsorbance height and high oil content sorbing material of intensity in water can be provided.
The specific embodiment
Below, successively to the manufacturing approach of oil content sorbing material of the present invention, oil content sorbing material and use the embodiment of the oil content recovery method of oil content sorbing material to describe.
(oil content sorbing material)
Oil content sorbing material in this embodiment is to constitute core by inorganic particulate, and polymer lining core and cohesion form.The invention is characterized in that with respect to the oil content sorbing material, the ratio of this inorganic particulate converts with volume and counts 50～97%, is preferably 70～90%, and the area of inorganic particulate that is present in the cross section of oil content sorbing material is whole 30～60%.
The ratio of inorganic particulate was less than 50% o'clock, and interparticle emptying aperture diminishes, and oil content can not be penetrated into inside, and therefore, the oil content adsorbance diminishes.In addition, the ratio of inorganic particulate surpasses at 97% o'clock, and amount of resin is very few, therefore, does not have and is used for the full intensity used at water.In addition, the area of inorganic particulate that is present in the cross section of oil content sorbing material is 30% when following, and the intensity of oil content sorbing material diminishes and is not suitable for practical application, greater than 60% o'clock, can keep the space of oil content to reduce, and the oil content adsorption capacity diminishes.
Through forming such structure, can when keeping oil content sorbing material intensity, make the maximization of oil content adsorbance.
With regard to the computational methods that volume converts, can calculate by the polymer solids composition in the raw material and particle solid constituent, can be under anaerobic state with more than the product by heating to 500 ℃ resinous principle all being volatilized, thereby the mensuration resin content is tried to achieve.In addition; The area that is present in the inorganic particulate in cross section can be through being embedded into the oil content sorbing material and cutting off the cross section obtain in embeding resins such as epoxy resin with observations such as SEM or light microscopes, and particle and material beyond it are carried out binaryzation (two stratification) and try to achieve.The sectional area of oil content adsorbent is for connecting the area that the inorganic particulate be present in gabarit forms, the area that calculates inorganic particulate shared ratio in this area.In addition, the prescribed threshold during binaryzation is the value of the briliancy of clearly distinguishing inorganic particulate and part beyond it.For example, can adopt the value of the peak-to-peak paddy part that is present in inorganic particulate and polymer brightness separately.
And then, preferably have more than the surface particle of oil content sorbing material and at the few incline structure of internal particle.The oil content sorbing material of hollow also can.When having such structure, owing to the space that has the storage oil content in inside, so the increase of oil content adsorbance, but because of the particle density of outside is high, so also can keep intensity.
So long as such oil content sorbing material, do not limit manufacturing approach is just special, when for example using spray-drying such as spray dryer, because power is inoperative when cohesion, so be easy to be manufactured on the agglomerate that can form the gap between particle.Particularly; Boiling point than solvent is high more than 30 ℃, when carrying out spray-drying under the preferred high temperature more than 50 ℃, through violent drying, and surperficial instantaneous formation; Inner residual solvent can expand and break-through, can be manufactured on top layer and the inner particle that has the particle density difference thus.
Because inorganic particulate forms the core of oil content sorbing material, therefore, even can not cause than suitably select in the material of big chemical change from the dipping of short time water yet.
For example can use: ceramic particle such as fused silica, crystallinity silica, glass, talcum, aluminium oxide, calcium silicates, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, aluminium nitride, magnesia, beryllium oxide, mica or, aluminium, iron, copper and their metallics such as alloy; Or as their magnetic iron ore, ilmenite, magnetic iron ore, magnesia ferrite, Conjugate ferrite, Ni ferrite, barium ferrite etc. of oxide.
In addition, for metallic,, therefore preferably comprise magnetic because it is favourable when reclaiming the oil content sorbing material.
Magnetic is not special to be limited, and is preferably under room temperature region, to show ferromagnetic material.But; In this embodiment; Be not limited to these materials, can use all ferromagnetic substances, for example can enumerate: iron and comprise alloy, magnetic iron ore, ilmenite, magnetic iron ore, magnesia ferrite, Conjugate ferrite, Ni ferrite, barium ferrite of iron etc.
Wherein, if the ferrite based compound of the excellent in stability in water then can more effectively be realized the present invention.For example magnetic iron ore is tri-iron tetroxide (Fe 3O 4) not only cheap, even and also very stable as magnetic in water, also very safe as element, thus be used for water treatment easily, so preferred.
With regard to the size or shape of magnetic, the area in cross section is 30～60% when needing only as agglomerate, and any magnetic can.The average grain diameter of preferred magnetic is 0.05～100 μ m, further is preferably 0.5～5 μ m.At this, average grain diameter records through laser diffractometry.Particularly, can measure through SALD-DS21 type determinator (Shimadzu Seisakusho Ltd.'s system) etc.
The average grain diameter of magnetic is during greater than 100 μ m, and the particle of cohesion becomes excessive, when carrying out the oil content recovery process; Tendency with the dispersion variation in water, in addition, the effective surface area of particle reduces; Has the tendency that the adsorbance of oils etc. reduces, so not preferred.In addition, average grain diameter is during less than 0.05 μ m, and primary particle condenses densely, has the tendency that can not obtain sufficient oil content adsorption space, degradation, so not preferred.At this, use the term of primary particle, secondary aggregation body for ease of explanation.Primary particle is meant single particle and has the particle of sphere, polyhedron, irregular shape, and in addition, the secondary aggregation body is meant the primary particle cohesion and the material that obtains, and is equivalent in meaning with oil content sorbing material of the present invention.
In addition, above-mentioned average grain diameter is not limited to the situation of magnetic, and is also preferred to inorganic particulates such as above-mentioned ceramic particle or nonmagnetic metallic, brings into play same action effect.
In addition; In this embodiment, the polymer of the core of the oil content sorbing material that lining is made up of above-mentioned inorganic particulate etc. is so long as the polymer of absorption oil content; Any polymer can; But when the skeleton of polymer was at least a polymer that has in styrene, butadiene, isoprene, acrylonitrile, alkyl acrylate, the alkyl methacrylate, the oil content absorption property was high, thereby preferred.
(manufacturing of oil content sorbing material)
Then, the manufacturing approach to the oil content sorbing material of above-mentioned embodiment describes.
At first, prepare above-mentioned inorganic particulate etc., polymer and solvent orange 2 A, they are mixed the pulp solution for preparing regulation.
Solvent orange 2 A be so long as can form dissolve polymer and be dispersed with just not special qualification of material of the pulp solution of inorganic particulate, but preferably is defined as polar solvent.The polar solvent hydrophily is excellent, and the hydroxyl that therefore exists with surface trace at inorganic particulate etc. is affine, inorganic particulate etc. can not condensed and is evenly dispersed in the polar solvent.
Need to prove that in this embodiment, " hydrophily " is defined as with water freely mixed; Particularly, be meant under 20 ℃ of 1 air pressure, temperature, under situation that the pure water of same capability slowly mixes; After mobile the calming down, this mixed liquor is also kept uniform outward appearance.
As hydrophilic solvent, can enumerate: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, acetone, oxolane etc.Preferably can dissolve acetone, the oxolane of various polymer.
On the other hand, when solvent orange 2 A was defined as non-polar solven, solvent orange 2 A was hydrophobic solvent (solubility that is defined as water is the material below 10%), and therefore, inorganic particulate condenses and becomes inhomogeneous in pulp solution sometimes.Therefore; Below utilizing, the spray dryer of explanation is made under the situation of oil content sorbing material; The material of inorganic particulate etc. occurs not comprising or only comprise the material of inorganic particulate etc.,, need a lot of operations in order to distinguish the substandard products that are not suitable for actual oil content absorption.And, because the composition of substandard products is also inhomogeneous, therefore when utilizing again,, be necessary defective products is carried out composition analysis so that its solution concentration is remained on setting value, thereby the operation of utilizing again becomes miscellaneous in order to turn back to pulp solution.
Then, the pulp solution that obtains is carried out spray-drying.In this spray-drying, thereby use can be removed organic solvent and obtains emboliform organic spray drying process from so-called containing the organic solution.In this embodiment, above-mentioned organic matter for above-mentioned inorganic particulate etc. as core, with resin composite body particle that above-mentioned polymer lining obtains around it, be oil content sorbing material of the present invention.
According to spray drying process; Through adjusting spray-dired environment temperature and spouting velocity etc.; Not only can adjust the average grain diameter that primary particle condenses the secondary aggregation body that obtains; And, between the primary particle after cohesion, forming the hole when removing organic solvent, also can easily form as the oil content sorbing material and preferred porous structure.
In addition, preferably the boiling point than solvent orange 2 A is high more than 30 ℃ for the environment temperature the during spray-drying of spray dryer.This be because can be from the oil content granule for absorbing evaporating solvent A apace, before the solvent evaporates of inside, form gabarit, thereby between inside and gabarit, form the density contrast that exists of primary particle.
Than 30 ℃ low the time, the formation of this gabarit is slack-off, and solvent is basic to volatilize with inside simultaneously, so is difficult to form density contrast sometimes.
Spray drying process can adopt known any means, can enumerate for example collar plate shape, pressurized nozzles type, two-fluid spray nozzle type.
(oil content recovery method)
Then, the oil content recovery method that has used above-mentioned oil content sorbing material is described.The oil content recovery is meant from the water that comprises oil content and separates oil content.Be meant in the organic matter that is mixing/be scattered in the water at this " oil content ", general at normal temperatures for liquid, be insoluble in water, viscosity higher, than the low material of the proportion of water.More specifically, be of animal or plant nature grease, hydrocarbon, fragrant wet goods.It is representative with fatty glyceride, oil, higher alcohol etc.These oils have characteristic at the aspects such as functional group that have separately, therefore can select to constitute the polymer or the functional group of above-mentioned oil content sorbing material according to its characteristic.
At first, the oil content sorbing material is flooded, is dispersed in the water that comprises oil content.As stated, on the surface of oil content sorbing material, owing to molecular structure forms oil loving polymer, therefore, through the compatibility of polymer and oil content, oil content is adsorbed on the above-mentioned polymer.At this moment, the air spots of oil content sorbing material is sliding, when being preferably loose structure, and the adsorption efficiency of oil content uprises.As stated, when using spray drying process to make the oil content sorbing material,, therefore must improve the adsorption efficiency of oil content than being easier to form porous matter.
Behind the oil content sorbing material absorption oil content, the oil content sorbing material is separated from water, separate and remove the oil content that is present in the water.In addition, when separating the oil content sorbing material, can pass through known method, the Shen that for example above-mentioned gravity brings falls or in cyclone separator etc., utilizes centrifugal force easily to carry out.And then, comprise under the situation of magnetic at inorganic particulate etc., also can and with the separation that utilizes magnetic force to carry out.
Do not limit as the water of oil content recycling object is special.Particularly, can use industrial water drainage, sewage, living drainage etc.The concentration of oil that is comprised in the water of handling is not special yet to be limited.
Then, after utilizing oil content sorbing material absorption oil content and it being removed, the oil content sorbing material is cleaned the oil content of removing absorption from water with solvent B.This solvent B is necessary for the material that can not dissolve the polymer that uses in the oil content sorbing material.Particularly, use the solubility in solvent B to be the material below the 1000mg/L.
Such solvent is according to the difference of polymer that is covered or finishing and difference for example can be enumerated: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, butanols, isobutanol, hexanol, cyclohexanol or acetone, MEK, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Anaesthetie Ether, isopropyl ether, butyl oxide, oxolane 、 diox, cyclohexane, chloroform, dimethylaniline, freon, n-hexane, cyclohexanone, toluene, xylenes etc.
Wherein, preferred especially nonpolar solvent.Nonpolar solvent shows hydrophobicity, and particularly the compatibility with oil content uprises, and therefore, can clean above-mentioned oil content adsorbed on the above-mentioned oil content sorbing material simple and easy and effectively.In addition, under the situation of using non-polar solven, the separation of the sorbing material of deterioration is removed and is become very easy.Need to prove that the solubility that " hydrophobicity " is defined as water is below 10% and separated form water.Hexane particularly because, boiling point high to the dissolving power of oil also is about 70 degree, normally stable liquid at room temperature, is therefore handled easily, thereby preferred.
In addition, as solvent B, also can preferably use alcohol.In this case, be easy to replace, remove the impurity beyond the oil content easily with the water that adheres to or be adsorbed on oil content sorbing material surface.In alcohols, preferred especially low-boiling methyl alcohol and ethanol.
In this operation, can enumerate the oil content sorbing material for example is filled in the post, portion is through the method for solvent B within it; Or particularly comprise under the such situation of magnetic at the oil content sorbing material, when being put into rinse bath, drops into the oil content sorbing material a large amount of solvent B, make the method for its separation with methods such as cyclone separator or magnetic force.
Embodiment
Below, based on embodiment the present invention is specified.
(embodiment 1)
With polystyrene (G590; Japan Polystyrene Co., Ltd. system, density 1.05g/cm 3) 6 weight portions are dissolved in the oxolane of 300ml and process solution, are octahedra tri-iron tetroxide particle 40 weight portion (the density 5.0g/cm of 1000nm with average grain diameter 3, specific area 3.0m 2/ g) be distributed in this solution, obtain composition.
Use disk (B-290 type; Bavin field section length of schooling) under 100 ℃, said composition is sprayed, made the resin composite body that to condense glomerate average aggregate particle size be about 20 μ m, i.e. the oil content granule for absorbing.
Carry out the result that SEM observes, the oil content granule for absorbing becomes porous body.Get the SEM photo in oil content granule for absorbing cross section, carry out binaryzation, try to achieve particle density, the particle area is 60% as a result, has the particle space, that have the particle density difference in the middle of obtaining.
Use slight compression testing machine (MCT-W500; Shimadzu Scisakusho Ltd's system) measure the compressive strength of this particle, the result is 2.2MPa.In addition, (ベ ニ サ Application ミ シ Application oil: drop into the composition of 0.1g in 20ml water B-111), stirs after 1 minute, investigate concentration of oil in the water, the result learns and is adsorbed with 99.6% oil comprising the machine oil of 5000ppm.
Above result is summarised in the table 1.With regard to outside with inner density contrast, ◎ representes hollow, and zero expression is tilted, and * expression does not have basically.With regard to particle intensity, ◎ representes that compressive strength is more than the 2MPa, and zero expression is not defeated and dispersed through in water, stirring, * be illustrated in the whipping process defeated and dispersed in water.With regard to the oil content adsorption rate, ◎ representes more than 99% that zero expression is more than 97% and be lower than 99%, and * expression is lower than 97%.
(embodiment 2～5)
Except changing amount of resin (containing ratio of inorganic particulate), likewise make sample with embodiment 1.The result is shown in table 1.When amount of resin tailed off (inorganic particulate contain quantitative change many), the direction particle with cross section tailed off, and the tendency of emptying aperture occurs.Amount of resin oil content adsorption rate less is good more.
(comparative example 1)
Except amount of resin is become the 0.1g, likewise make sample with embodiment 1.The result is shown in table 1.Said composition forms the shape of agglomerate at once after spray-drying, defeated and dispersed when in water, stirring, and becomes primary particle basically.Can not measure the oil content adsorbance.
(comparative example 2)
Except amount of resin is become the 10g, likewise make sample with embodiment 1.The result is shown in table 1.On the cross section of said composition, though have difference in the inner density that exists with outside inorganic particulate, the some in the gap between the inorganic particulate on the surface of composition is by landfill.The result who measures the oil content adsorption rate is 96.9%.
(embodiment 6～8)
Except changing vapo(u)rizing temperature, likewise make sample with embodiment 1.The result is shown in table 1.During the rising temperature, the density that exists of the inorganic particulate in the cross section of composition occurs, and when in vapo(u)rizing temperature being (boiling point+63.5 ℃) more than 120 ℃, general half is a hollow-particle, and when vapo(u)rizing temperature was 140 ℃, about seventy percent was hollow-particle.Oil content adsorption rate ratio is the sample height of made at a lower temperature.
(comparative example 3)
Except vapo(u)rizing temperature being become 55 ℃ (boiling points-1.5 ℃), likewise make sample with embodiment 1.The result is shown in table 1.When reducing temperature, the density that exists of the inorganic particulate in the cross section of composition can not occur tilting, and becomes the composition at obstruction to middle part.The oil content adsorption rate is than low 75 ℃ of following manufactured samples.
(embodiment 10～17)
In embodiment 10～15, change the kind and the amount of polymer respectively, in embodiment 16,17, change the kind of inorganic particulate, vapo(u)rizing temperature is made as 120 ℃, in addition, likewise make sample with embodiment 1.The result is shown in table 1.As long as the inorganic particulate in content and the cross section of control inorganic particulate have a ratio, even the kind of change polymer or inorganic particulate has also obtained oil content adsorbance height and the high composition of intensity.
Figure BPA00001499656900101

Claims (5)

1. an oil content granule for absorbing is characterized in that,
It has inorganic particulate and is formed at the polymer between this inorganic particulate surface or this inorganic particulate,
The containing ratio of said inorganic particulate is 50 volume %～97 volume % with respect to said inorganic particulate and said polymer,
The area of said inorganic particulate is 30%～60% with respect to the cross section of said inorganic particulate and said polymer.
2. oil content granule for absorbing according to claim 1 is characterized in that, the density of said inorganic particulate along with from the surface of said oil content granule for absorbing to inner and diminish.
3. oil content granule for absorbing according to claim 1 is characterized in that, said inorganic particulate is a metal oxide.
4. oil content granule for absorbing according to claim 2 is characterized in that, said inorganic particulate is a metal oxide.
5. the manufacturing approach of an oil content granule for absorbing, it possesses:
Inorganic particulate, polymer and solvent are modulated the operation of pulp solution; With
The operation of said pulp solution being sprayed under than the high temperature environment more than 30 ℃ of boiling point of said solvent.
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